Chain transfer agent, photosensitive composition, cured product of photosensitive composition, and method for curing photosensitive composition

Abstract

There are provided a photosensitive composition, and a cured product of the photosensitive composition, the photosensitive composition being an ultraviolet curable composition that is curable in a short time while a portion of the photosensitive composition such as a dark portion where radicals are not generated at all is curable. A cured product is obtained by curing a photosensitive composition by ultraviolet irradiation, the photosensitive composition containing an ultraviolet curable material, and a chain transfer agent that contains an ingredient (a) that is a compound containing at least one kind selected from the group consisting of a urethane bond, a urea bond and an isocyanate group, and an ingredient (b) that is a metal-containing compound, wherein a portion of the composition where irradiation light does not reach is curable.

Claims

1. A photosensitive composition comprising: an ultraviolet curable material; and a chain transfer agent comprising: an ingredient (a) that comprises a compound comprising at least one selected from the group consisting of a urethane bond, a urea bond, and an isocyanate group; and an ingredient (b) that comprises a metal-containing compound, wherein: a portion of the composition where irradiation light does not reach is curable; the composition is not moisture-curable; the chain transfer agent does not contain a thermal radical generating agent; and a mass ratio of the ingredient (a) to the ingredient (b) is in a range of from 100:0.001 to 100:1.

2. The photosensitive composition according to claim 1, wherein a ratio between the ultraviolet curable material and the chain transfer agent is within a range from 90:10 to 10:90.

3. The photosensitive composition according to claim 1, wherein the metal-containing compound is a tin-containing compound, or a compound comprising at least one metal selected from the group consisting of zinc, cobalt, and nickel, the tin-containing compound being selected from the group consisting of bis(2,4-pentanedionato)tin, dibutyltin bis(trifluoromethanesulfonate), dibutyltin diacetate, dibutyltin maleate, phthalocyaninetin(IV) dichloride, tetrabutyl ammonium difluoro triphenyltin, tin(II) phthalocyanine, tributyl(2-pyridyl)tin, tributyl(2-thienyl)tin, tributyltin acetate, tributyl(trimethylsilylethinyl)tin, and trimethyl(2-pyridyl)tin.

4. The photosensitive composition according to claim 1, wherein the mass ratio of the ingredient (a) and the ingredient (b) is in a range of from 100:0.001 to 100:10.

5. A cured product that comprises the photosensitive composition according to claim 1 that is cured.

6. A photosensitive composition comprising: an ultraviolet curable material; a chain transfer agent; and an ultraviolet transmission inhibitor to inhibit ultraviolet transmission, wherein: the chain transfer agent comprises an ingredient (a) that comprises a compound comprising at least one selected from the group consisting of a urethane bond, a urea bond, and an isocyanate group, and an ingredient (b) that comprises a metal-containing compound; the composition is not moisture-curable; the chain transfer agent does not contain a thermal radical generating agent; and a mass ratio of the ingredient (a) to the ingredient (b) is in a range of from 100:0.001 to 100:1.

7. The photosensitive composition according to claim 6, wherein the metal-containing compound is a tin-containing compound, or a compound comprising at least one metal selected from the group consisting of zinc, cobalt, and nickel, the tin-containing compound being selected from the group consisting of bis(2,4-pentanedionato)tin, dibutyltin bis(trifluoromethanesulfonate), dibutyltin diacetate, dibutyltin maleate, phthalocyaninetin(IV) dichloride, tetrabutyl ammonium difluoro triphenyltin, tin(II) phthalocyanine, tributyl(2-pyridyl)tin, tributyl(2-thienyl)tin, tributyltin acetate, tributyl(trimethylsilylethinyl)tin, and trimethyl(2-pyridyl)tin.

8. The photosensitive composition according to claim 6, wherein the mass ratio of the ingredient (a) and the ingredient (b) is in a range of from 100:0.001 to 100:10.

9. A cured product that comprises the photosensitive composition according to claim 6 that is cured by an ultraviolet curing reaction.

10. The photosensitive composition according to claim 2, wherein the metal-containing compound is a tin-containing compound, or a compound comprising at least one metal selected from the group consisting of zinc, cobalt, and nickel, the tin-containing compound being selected from the group consisting of bis(2,4-pentanedionato)tin, dibutyltin bis(trifluoromethanesulfonate), dibutyltin diacetate, dibutyltin maleate, phthalocyaninetin(IV) dichloride, tetrabutyl ammonium difluoro triphenyltin, tin(II) phthalocyanine, tributyl(2-pyridyl)tin, tributyl(2-thienyl)tin, tributyltin acetate, tributyl(trimethylsilylethinyl)tin, and trimethyl(2-pyridyl)tin.

11. The photosensitive composition according to claim 7, wherein the mass ratio of the ingredient (a) and the ingredient (b) is in a range of from 100:0.001 to 100:10.

12. A cured product that comprises the photosensitive composition according to claim 11 that is cured by an ultraviolet curing reaction.

13. The photosensitive composition according to claim 1, wherein the ingredient (a) of the chain transfer agent comprises a compound comprising a urethane bond.

14. The photosensitive composition according to claim 6, wherein the ingredient (a) of the chain transfer agent comprises a compound comprising a urethane bond.

15. The photosensitive composition according to claim 1, wherein: the ingredient (a) is a mixture of a polyisocyanate compound and a (meth)acrylate of a polyol; and the mass ratio of the ingredient (a) to the ingredient (b) is in a range of from 100:0.001 to 100:0.5.

16. The photosensitive composition according to claim 1, wherein the chain transfer agent does not contain a mercapto group.

17. The photosensitive composition according to claim 1, wherein the metal-containing compound is selected from the group consisting of bis (2,4-pentanedionato)tin, dibutyltin bis(trifluoromethanesulfonate), dibutyltin diacetate, dibutyltin maleate, phthalocyaninetin(IV) dichloride, tetrabutyl ammonium difluoro triphenyltin, tin(II) phthalocyanine, tributyl(2-pyridyl)tin, tributyl(2-thienyl)tin, tributyltin acetate, tributyl(trimethylsilylethinyl)tin, trimethyl(2-pyridyl)tin, bis(hexafluoroacetylacetonato)copper(II) salt, bis(2,4-pentanedionato)copper(II), bis(1,3-propanediamine)copper(II)dichloride, bis(8-quinolinolate)copper(II), bis(trifluoro-2,4-pentanedionato)copper(II), copper(II) bis(2-hydroxyethyl)dithiocarbamate, copper diethyldithiocarbamate, copper(II) dimethyldithiocarbamate, ethylenediaminetetraacetic acid copper(II)disodium salt, phthalocyanine copper(II), dichloro(1,10-phenanthroline)copper(II), phthalocyanine copper, tetra-4-tert-butylphthalocyanine copper, tetrakis(acetonitrile)copper(I) hexafluorophosphate, bis[2-(2-benzothiazolyl)phenolato]zinc(II), bis[2-(2-benzoxazolyl)phenolato]zinc(II), bis(2-hydroxyethyl)dithiocarbamic acid]zinc(II) salt, bis(2,4-pentanedionato)zinc(II), bis(8-quinolinolate)zinc(II), bis(tetrabutylammonium) bis(1,3-dithio1-2-thione-4,5-dithiolato)zinc complex, ethylenediaminetetraacetic acid disodium zinc salt, zinc(II) dibenzyldithiocarbamate, zinc(II) dibutyldithiocarbamate, zinc diethyldithiocarbamate, zinc dimethyldithiocarbamate, phthalocyanine zinc, bis(cyclopentadienyl)cobalt(III) hexafluorophosphate, [1,1-bis(diphenylphosphino)ferrocene]cobalt(II) dichloride, bis(hexafluoroacetylacetonato)cobalt(II), (1R,2R)-N,N-bis[3-oxo-2-(2,4,6-trimethylbenzoyl)butylidene]-1,2-diphenylethylenediaminato cobalt(II), (1S,2S)-N,N-bis[3-oxo-2-(2,4,6-trimethylbenzoyl)butylidene]-1,2-diphenylethylenediaminato cobalt(II), bis(2,4-pentanedionato)cobalt(II), bis(trifluoro-2,4-pentanedionato)cobalt(II), phthalocyanine cobalt(II), ethylenediaminetetraacetic acid disodium cobalt salt, hexaamminecobalt(III) chloride, N,N-disalicylalethylenediamine cobalt(II), [5,10,15,20-tetrakis(4-methoxyphenyl) porphyrinato]cobalt(II), tris(2,4-pentanedionato)cobalt(III), [1,2-bis(diphenylphosphino)ethane]nickel(II) dichloride, bis(dithiobenzil)nickel(II), bis(hexafluoroacetylacetonato)nickel(II), bis(2,4-pentanedionato)nickel(II), bis(tetrabutylammonium) bis(maleonitriledithiolato)nickel(II) complex, bis(tricyclohexylphosphine)nickel(II) dichloride, bis(triphenylphosphine)nickel(II) dichloride, bromo[(2,6-pyridinediyl)bis(3-methyl-l-imidazolyl-2-ylidene)]nickel bromide, ethylenediaminetetraacetic acid disodium nickel(II) salt, nickel(II) dibutyldithiocarbamate, and nickel diethyldithiocarbamate.

18. The photosensitive composition according to claim 1, wherein the metal-containing compound is selected from the group consisting of bis(2,4-pentanedionato)zinc(II), zinc (II) diethyldithiocarbamate, bis(2,4-pentanedionato)cobalt(II), and nickel(II) dibutyldithiocarbamate.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a chart showing a result of ESR measurement of a chain transfer agent (B-2).

(2) FIG. 2 is a graph showing a relation between a peak strength of the ESR measurement of the chain transfer agent and an amount of time when the chain transfer agent is left at room temperature.

(3) FIG. 3 is a chart showing a measurement result of FT-IR of double bonds of an acrylate.

EMBODIMENTS FOR CARRYING OUT THE INVENTION

(4) Hereinafter, a detailed description according to preferred embodiments of the present invention will be provided. A chain transfer agent according to a preferred embodiment of the present invention contains an ingredient (a) that defines a compound having nitrogen atoms and oxygen atoms and containing one or more pieces of at least one kind selected from the group consisting of a urethane bond, a urea bond, and an isocyanate group in its molecules (also referred to as a compound containing one or more pieces of a urethane bond, a urea bond, and an isocyanate group), and an ingredient (b) that defines a metal-containing compound.

(5) By being added to a radical polymerizable material, the chain transfer agent according to the present invention instantaneously is capable of transferring radicals to a site in the radical polymerizable material where radicals are not generated, and initiating to progress a polymerization reaction at the site. To be specific, the chain transfer agent according to the present invention is used by being added to a radical polymerizable material, and is capable of improving a curing property of the radical polymerizable material. An ultraviolet curable material is preferably used as the radical polymerizable material.

(6) As the ingredient (a) that defines the compound containing one or more pieces of the urethane bond, the urea bond, and the isocyanate group, a conventionally known compound can be used without limitation as long as the compound contains one or more pieces of at least one kind selected from the group consisting of a urethane bond indicated by the (formula 1) below, a urea bond indicated by the (formula 2) below, and an isocyanate group indicated by the (formula 3) below in its molecules.
NHCOO(Formula 1)
NHCONH(Formula 2)
NCO(Formula 3)

(7) Specific examples of the compound containing one or more pieces of the urethane bond, the urea bond, and the isocyanate group include polyurethane of a variety of kinds, polyurea of a variety of kinds, and an isocyanate-containing compound. Each of the polyurethane of a variety of kinds and the polyurea of a variety of kinds is obtained by reacting the following isocyanate-containing compound, hydroxyl group (OH)-containing compound, and amine (NH2) containing compound.

(8) A compound containing the above-described isocyanate group indicated by the (formula 3) can be used as it is as the isocyanate-containing compound. Alternatively, the isocyanate-containing compound can be used as polyurethane of a variety of kinds and polyurea of a variety of kinds by being reacted with the following hydroxyl group-containing compound and amine containing compound.

(9) Examples of the isocyanate-containing compound include compounds such as an aliphatic isocyanate including a methylene diisocyanate, an ethylene diisocyanate, a tetramethylene diisocyanate, a hexamethylene diisocyanate (HDI), a dodecamethylene diisocyanate, a 2,2,4-trimethylhexane methylene diisocyanate, a lysine diisocyanate (LDI), and a 1,3,6-hexamethylene triisocyanate, compounds such as an alicyclic isocyanate including a hydrogenated-4,4-diphenyl methane diisocyanate (hydrogenated MDI), a hydrogenated-xylylene diisocyanate (hydrogenated XDI), a 1,4-cyclohexane diisocyanate, a hydrogenated-2,4-tolylenediisocyanate (hydrogenated TDI), an isophorone diisocyanate (IPDI), and a norbornene diisocyanate (NBDI), compounds such as an aromatic aliphatic isocyanate including a xylylene diisocyanate (XDI), and a tetramethylene xylylene diisocyanate (TMXDI), and compounds such as a polyisocyanate such as aromatic isocyanate including a 1,4-diphenyl diisocyanate, a 2,4 or 2,6-tolylenediisocyanate (TDI), a 2,4 or 4,4-diphenyl methane diisocyanate (MDI), a 1,5-naphthalene diisocyanate (NDI), a 3,3-dimethyl-4,4-diphenyl methane diisocyanate, an O-tolidine diisocyanate, a polyphenyl methane polyisocyanate (crude MDI), a triphenyl methane triisocyanate, and a tris(isocyanatophenyl)thiophosphate, and further include biuret type isocyanates that are obtained by reacting these polyisocyanates with water, adduct type polyisocyanates that are obtained by reacting these polyisocyanates with polyvalent alcohol such as trimethylolpropane, a liquid prepolymer that is obtained by polymerizing a portion of a polyvalent isocyanate with polyester or a polyether derivative, and polymers that are obtained by isocyanurating these polyisocyanates. Among these isocyanate-containing compounds, a single kind of isocyanate-containing compound may be used alone, or two or more kinds of isocyanate-containing compounds may be used in combination.

(10) Examples of the hydroxyl group-containing compound that is reacted with the isocyanate-containing compound in order to obtain polyurethane of a variety of kinds include alcohols with carbon chains having 1 to 30 carbon atoms having hydroxyl groups at their terminals, (poly)ethylene glycol of terminal diol, (poly)propylene glycol of terminal diol, (poly)hexamethylene glycol of terminal diol, (poly)caprolactone of terminal diol, (poly)ester (poly)ol of terminal diol, (poly)amide of terminal diol, and (poly)ester of terminal dial.

(11) The polyurethane of a variety of kinds does not have to be in the form of a liquid as long as the polyurethane of a variety of kinds is dissolved or in a suspended form when blended finally in the curable material; however, it is preferable that the polyurethane of a variety of kinds should be in the form of a liquid from the viewpoint of easy blending, and that a liquid compound having a molecular weight equal to or less than 100,000 should be used as the hydroxyl group-containing compound when using the polyurethane of a variety of kinds in the form of a liquid.

(12) Examples of the amine containing compound that is reacted with the isocyanate-containing compound in order to obtain polyurea of a variety of kinds include amines with carbon chains having 1 to 30 carbon atoms having primary or secondary amino group at their terminals, (poly)ethylene glycol of terminal diamine, (poly)propylene glycol of terminal diamine, (poly)hexamethylene glycol of terminal diamine, (poly) caprolactone of terminal diamine, (poly)ester (poly)ol of terminal diamine, (poly)amide of terminal diamine, and (poly)ester of terminal diamine.

(13) The polyurea of a variety of kinds does not have to be in the form of a liquid as long as the polyurea of a variety of kinds is dissolved or in a suspended form when blended finally in the curable material; however, it is preferable that the polyurea of a variety of kinds should be in the form of a liquid from the viewpoint of easy blending, and that a liquid compound having a molecular weight equal to or less than 100,000 should be used as the amine containing compound when using the polyurea of a variety of kinds in the form of a liquid.

(14) In addition, it is preferable that the terminal groups in the polyurethane compound and the polyurea compound should be sealed with an alkyl group, a (meth)acrylic group, an epoxy group, an oxazolyl group, a carbonyl group, a thiol group, a thioether group, a thioester group, an (ester) phosphate group, a phosphonate (ester) group, and a carboxylate (ester) group by (thio)ether, (thio)ester,amido, (thio)urethane, (thio)urea and an N-alkyl link as necessary.

(15) It is also preferable that the urethane bond, the urea bond, and the isocyanate group should be contained in molecules while a plurality of kinds of the urethane bond, the urea bond, and the isocyanate group are bonded, or while the terminal groups of the urethane bond, the urea bond, and the isocyanate group are combined.

(16) It is preferable that one kind or a plurality of metals selected from the group consisting of tin, copper, zinc, cobalt, and nickel should be used as the metal-containing compound of the ingredient (b) that is combined with the compound containing one or more pieces of the urethane bond, the urea bond, and the isocyanate group to make up the chain transfer agent. A conventionally known metal-containing compound can be used as the metal-containing compound of the ingredient (b) without special limit as long as the one kind or the plurality of metals described above are contained in molecular in the form of metal salt or metal complex.

(17) Examples of the metal salt include metal salts in the form of carboxylate salt, phosphoric salt, salt of sulfonic acid, hydrochloride salt, bromate salt, and (per) chlorate, and chlorite of the above descried metals

(18) A conventionally known metal complex can be used as the metal complex without special limit as long as the metal complex is coordinated at 1:1 to 1:4 (metal: ligand) with an organic ligand that can be coordinated with the above-described metals and is stabilsed.

(19) Specific examples of the metal-containing compound of the ingredient (b) include bis(2,4-pentanedionato)tin, dibutyltin bis(trifluoromethanesulfonate), dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, phthalocyaninetin(IV)dichloride, tetrabutyl ammonium difluoro triphenyltin, tin(II) phthalocyanine, tributyl(2-pyridyl)tin, tributyl(2-thienyl)tin, tributyltin acetate, tributyl(trimethylsilylethinyl)tin, trimethyl(2-pyridyl)tin, bis(hexafluoroacetylacetonato)copper(II) salt, bis(2,4-pentanedionato)copper(II), bis(1,3-propanediamine)copper(II)dichloride, bis(8-quinolinolate)copper(II), bis(trifluoro-2,4-pentanedionato)copper(II), copper(II)bis(2-hydroxyethyl)dithiocarbamate, copper diethyldithiocarbamate, copper(II) dimethyldithiocarbamate, ethylenediaminetetraacetic acid copper(II)disodium salt, phthalocyanine copper(II), dichloro(1,10-phenanthroline)copper(II), phthalocyanine copper, tetra-4-tert-butylphthalocyanine copper, tetrakis(acetonitrile)copper(I) hexafluorophosphate, copper naphthenate, bis[2-(2-benzothiazolyl)phenolato]zinc(II), bis[2-(2-benzoxazolyl)phenolato]zinc(II), bis(2-hydroxyethyl)dithiocarbamic acid]zinc(II) salt, bis(2,4-pentanedionato)zinc(II), bis(8-quinolinolate)zinc(II), bis(tetrabutylammonium)bis(1,3-dithiol-2-thione-4,5-dithiolato)zinc complex, ethylenediaminetetraacetic acid disodium zinc salt, zinc(II)dibenzyldithiocarbamate, zinc(II)dibutyldithiocarbamate, zinc diethyldithiocarbamate, zinc dimethyldithiocarbamate, phthalocyanine zinc, zinc naphthenate, bis(cyclopentadienyl)cobalt(III) hexafluorophosphate, [1,1-bis(diphenylphosphino)ferrocene]cobalt(II)dichloride, bis(hexafluoroacetylacetonato)cobalt(II), (1R,2R)N,N-bis[3-oxo-2-(2,4,6-trimethylbenzoyl) butylidene]-1,2-diphenylethylenediaminato cobalt(II), (1S,2S)N,N-bis[3-oxo-2-(2,4,6-trimethylbenzoyl) butylidene]-1,2-diphenylethylenediaminato cobalt(II), bis(2,4-pentanedionato)cobalt(II), bis(trifluoro-2,4-pentanedionato)cobalt(II), phthalocyanine cobalt(II), ethylenediaminetetraacetic acid disodium cobalt salt, hexaamminecobalt(III) chloride, N,N-disalicylalethylenediamine cobalt(II), [5,10,15,20-tetrakis(4-methoxyphenyl) porphyrinato]cobalt(11), tris(2,4-pentanedionato)cobalt(III), cobalt naphthenate, [1,2-bis(diphenylphosphino)ethane]nickel(II) dichloride, bis(dithiobenzil)nickel(II), bis(hexafluoroacetylacetonato)nickel(II), bis(2,4-pentanedionato)nickel(II), bis(tetrabutylammonium)bis(maleonitriledithiolato)nickel(II) complex, bis(tricyclohexylphosphine)nickel(II) dichloride, bis(triphenylphosphine)nickel(II) dichloride, bromo[(2,6-pyridinediyl)bis(3-methyl-1-imidazolyl-2-ylidene)]nickel bromide, ethylenediaminetetraacetic acid disodium nickel (II) salt, nickel(II) dibutyldithiocarbamate, and nickel diethyldithiocarbamate. Among these metal-containing compounds, a single kind of metal-containing compound may be used alone, or two or more kinds of metal-containing compounds may be used in combination.

(20) Examples of the form of the metal-containing compound of the ingredient (b) include the forms of organic acid salt and metal complex because the metal-containing compounds in the form of organic acid salt and metal complex are easy to blend and prevent precipitation during storage while not having to have high solubility in an organic substance as long as the metal-containing compounds become uniform eventually in the radical polymerizable material.

(21) The metal-containing compound of the ingredient (b) is capable of making up the chain transfer agent by being combined with the compound containing the urethane bond, the urea bond, or the isocyanate group of the ingredient (a).

(22) A method for combining the ingredient (a) and the ingredient (b) is not limited specifically, and it is essential only that both the ingredients should be blended at room temperature or while heating; however it is preferable that both the ingredients should be sufficiently agitated or blended to be dissolved or uniformly dispersed with the use of an agitation equipment such as a blender at appropriate temperature under reduced pressure or in an inert gas atmosphere such as a nitrogen atmosphere.

(23) It is preferable that the ratio between the ingredient (a) and the ingredient (b) should be within a range from (a): (b)=100:0.001 to 100:10 at amass ratio. It is more preferable that the ratio between the ingredient (a) and the ingredient (b) should be within a range from (a):(b)=100:0.005 to 100:5 at a mass ratio. When the content of the metal-containing compound of the ingredient (b) is too large, the metal-containing compound becomes an insoluble matter to precipitate while the prepared chain transfer agent is stored, and when the insoluble matter remains in a reactant (polymerized material) of the radical polymerizable material, the physical properties of the polymerized material could be lost. In addition, because the ingredient (b) inhibits transmission of ultraviolet light when added to the ultraviolet curable material, the too large content of ingredient (b) could inhibit a curing reaction. On the other hand, when the content of the ingredient (b) is too small, the chain transfer agent cannot function perfectly as a complex to have a reduced function.

(24) It is preferable that the chain transfer agent according to the present invention should not contain a group having sulfur atoms such as a mercapto group and a disulfide group. This is because when the chain transfer agent is made up from a compound that does not contain sulfur atoms, there is not a problem of malodor when the compound is added to the radical polymerizable material.

(25) It is preferable that the chain transfer agent according to the present invention further contains various kinds of additives as necessary within a range of not impairing the object of the present invention. Examples of the additives include a stabilizer, a plasticizer, a softener, a coloring pigment, a colorant, an antistatic agent, a flame retardant, a sensitizer, a dispersing agent, a solvent, antibacterial agent, and a fungicide.

(26) Examples of the stabilizer include an antiaging agent, an antioxidant, and a dehydrating agent. Specific examples of the plasticizer include a hindered phenol compound, a hindered amine compound (antiaging agent), butylhydroxytoluene, butylhydroxytoluene, butylhydroxyanisole, triphenyl phosphite (antioxidant), and an acid chloride such as a maleic acid anhydride, an acid phthalic anhydride, a benzophenonetetracarboxylic dianhydride, calcined lime, a carbodiimide derivative, and oxychloride such as a stearyl chloride (dehydrating agent). In addition, a small amount of polymerization inhibitor such as methoquinone can be used as the stabilizer.

(27) It is to be noted that most of the stabilizers described above have a negative influence on the radical chain, so that it is preferable to add an extremely small amount of stabilizer.

(28) Examples of the plasticizer include dioctyl adipate, dibutyl sebacate, diethylhexyl sebacate, isodecyl succinate, diethylene glycol benzoate, a pentaerythritol ester, a butyl oleate, a methyl acetyl ricinolate, a tricresyl phosphate, a trioctyl phosphate, propylene adipate glycol polyester, butylene adipate glycol polyester, phenol, laurate, stearic acid, a docosanoic acid, a paraffinic oil, a napthenic oil, and an aromatic oil.

(29) Examples of the softener include vinyl group-containing lactam such as N-vinyl pyrrolidone and N-vinylcaprolactam, hydroxyl butyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, and 2-ethylhexyl vinyl ether.

(30) Examples of the coloring pigment include an inorganic coloring pigment such as titanium dioxide, zinc oxide, ultramarine, colcothar, lithopone, lead, cadmium iron, cobalt, aluminum, hydrochloride and sulfate salt, and an organic coloring pigment such as an azo pigment and a copper phthalocyanine pigment.

(31) Examples of the antistatic agent include a hydrophilic compound such as quaternized ammonium salt, polyglycol, and an ethylene oxide derivative.

(32) Examples of the flame retardant include a chloroalkyl phosphate, a dimethyl methyl phosphonate, a bromine/phosphorous compound, an ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether.

(33) Examples of the sensitizer include dimethylformamide, N-methylpyrrolidone, triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylamino benzoate, ethyl 4-dimethylamino benzoate, isoamyl 4-dimethylamino benzoate, and UBECRIL P102, 103, 104 and 105 (manufactured by UCB JAPAN CO. LTD.) that are commercialized products.

(34) Examples of the dispersing agent include a surface acting agent such as polyoxyethylene nonylphenyl ether, and polyethylene glycol octylphenyl ether.

(35) Examples of the solvent include any solvent as long as the solvent dissolves the chain transfer agent to reduce the viscosity of the chain transfer agent, or to increase the compatibility of the chain transfer agent. Specific examples of the solvent include a polar solvent such as tetrahydrofuran, dimethylformamide, ethyl acetate and methyl ethyl ketone, and a chlorinated solvent such as dichloroethane and trichlorobenzene.

(36) The additives of the variety of kind described above can be used in combination. A method for blending the additives is not limited specifically: however, it is preferable that the additives should be sufficiently agitated or blended to be dissolved or uniformly dispersed with the use of an agitation equipment such as a blender under reduced pressure or in an inert gas atmosphere such as a nitrogen atmosphere. In addition, it is also preferable that the additives should be added to a photosensitive composition without being added to the chain transfer agent.

(37) Hereinafter, a description of a photosensitive composition according to the present invention will be provided. The photosensitive composition contains (A) an ultraviolet curable material, and the chain transfer agent described above, and a portion of the composition where irradiation light such as ultraviolet light for curing the composition does not reach is curable. A known ultraviolet curable material can be used as (A) the ultraviolet curable material. To be specific, the ultraviolet curable material contains a basic composition that defines a blended material containing a curable monomer and oligomer such as liquid (meth)acrylate, and a photo polymerization initiator, and any ultraviolet curable material can be used as the ultraviolet curable material as long as a cured product of the photosensitive composition can be obtained by irradiating the photosensitive composition with ultraviolet light. It is to be noted that (meth)acrylate defines both methacrylate and acrylate in the present invention. According to the curing principle of the ultraviolet curable material, the photo polymerization initiator absorbs the ultraviolet light to generate an activated species such as a radical species, and the activated species radical polymerizes the carbon-carbon double bonds of the (meth)acrylate to cure the (meth)acrylate.

(38) It is preferable that the ratio between (A) the ultraviolet curable material and (B) the chain transfer agent should be within a range from (A):(B)=90:10 to 10:90 at a mass ratio. It is more preferable that the ratio between (A) the ultraviolet curable material and (B) the chain transfer agent should be within a range from (A):(B)=80:20 to 20:80 at a mass ratio. When the content of (B) the chain transfer agent is too large, the material ratio relating to ultraviolet curing becomes relatively small, and a sufficiently cured product cannot be obtained. On the other hand, when the content of (B) the chain transfer agent is too small, chain transfer capability becomes insufficient, so that the function of curing a dark portion of the ultraviolet curable material could be insufficient.

(39) Hereinafter, a detailed description of the ultraviolet curable material will be provided. The liquid (meth)acrylate compound is not limited specifically, and a conventionally known liquid (meth)acrylate compound can be used as long as the liquid (meth)acrylate compound is a compound that contains one or more (meth)acrylates in its molecules.

(40) Specific examples of the (meth)acrylate described above include mono(meth)acrylate such as isobornyl(meth)acrylate, bornyl(meth)acrylate, tricyclodecenyl(meth)acrylate, dicyclopentanyl(meth)acrylate, dicyclopentenyl(meth)acrylate, cyclohexyl(meth)acrylate, (meth)acrylic acid, benzyl(meth)acrylate, 4-butylcyclohexyl(meth)acrylate, (meth)acryloylmorpholine, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropy(meth)acrylate, 4-hydroxybutyl(meth)acrylate, methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, isopropyl(meth)acrylate, octyl(meth)acrylate, isoctyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate, undecyl(meth)acrylate, dodecyl(meth)acrylate, lauryl(meth)acrylate, stearyl(meth)acrylate, isostearyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxyethylene glycol(meth)acrylate, ethoxy ethyl(meth)acrylate, methoxy polyethylene glycol(meth)acrylate, methoxy polypropylene glycol(meth)acrylate, polyoxyethylene nonylphenyl ether acrylate, diacetone(meth)acrylamide, isobutoxymethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, t-octyl(meth)acrylamide, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, 7-amino-3,7-dimethyloctyl(meth)acrylate, N,N-diethyl(meth)acrylamide, and N,N-dimethyl aminopropyl(meth)acrylamide, and poly(meth)acrylate such as butanediol di(meth)acrylate, hexanediol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propane diol di(meth)acrylate, 2-hydroxy-3-acryloxy propyl methacrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tricyclodecan dimethylol di(meth)acrylate, 1,4-butanepolyoldi(meth)acrylate, 1,6-hexanepolyoldi(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorine, polyester di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanuratedi(meth)acrylate, tricyclodecan dimethylol di(meth)acrylate, an EO adduct of bisphenol A di(meth)acrylate, an EO adduct or a PO adduct of hydrogenated bisphenol A di(meth)acrylate, epoxy(meth)acrylate obtained by adding (meth)acrylate to diglycidyl ether of bisphenol A, triethylene glycol divinylether substance, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane EO adduct tri(meth)acrylate, tisacryloyloxyethyl phosphate, pentaerythritol tetra(meth)acrylate, tetrafurfuryl alcohol oligo(meth)acrylate, ethyl carbitol oligo(meth)acrylate, 1,4-butanediol oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate, trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, (poly)urethane(meth)acrylate, and (poly)butadiene(meth)acrylate. Among these (meth)acrylate, a single kind of (meth)acrylate may be used alone, or two or more kinds of (meth)acrylates may be used in combination.

(41) A polymeric photoinitiator can be added to the photosensitive composition. The photo polymerization initiator is not limited specifically, and a conventionally known photo polymerization initiator can be used as long as the photo polymerization initiator is a compound capable of absorbing ultraviolet light to initiate radical polymerization.

(42) Specific examples of the photo polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, ethyl anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4-dimethoxybenzophenone, 4,4-diaminobenzophenone, Michler's Ketone, benzoin propyl ether, benzoin ethyl ether, benzoin methyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-on, 2-hydroxy-2-methyl-1-phenylpropane-1-on, thioxanthone, diethyl thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-on, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, and bis-(2,6-dimethoxy benzoyl)-2,4,4-trimethylpentyl phosphine oxide. Among these photo polymerization initiators, a single kind of photo polymerization initiator may be used alone, or two or more kinds of photo polymerization initiators may be used in combination.

(43) Commercialized products such as IRGACURE 184, 369, 651, 500, 907, CGI1700, CGI1750, CGI1850, CG24-61; DAROCURE 1116, 1173, lucirinTPO (manufactured by BASF), and UBECRIL P36 (manufactured by UCB JAPAN CO. LTD.) can be used as the photo polymerization initiator.

(44) The photosensitive composition can contain, in addition to (A) the ultraviolet curable material and (B) the chain transfer agent, various kinds of additives as necessary within a range of not impairing the object of the present invention in order to obtain functions of a cured product. Examples of the additives include a stabilizer, a plasticizer, a softener, a coloring pigment, a colorant, an antistatic agent, a flame retardant, an adhesion-imparting agent, a sensitizer, a dispersing agent, a solvent, antibacterial agent, and a fungicide. Same additives exemplified as the additives for the chain transfer agent can be used as the additives for photosensitive composition. It is to be noted that most of the stabilizers described above have a negative influence on the radical chain reaction, so that it is preferable to add an extremely small amount of stabilizer.

(45) In particular, it is preferable that the photosensitive composition should contain (C) an ultraviolet transmission inhibitor arranged to inhibit ultraviolet transmission as the above-described additive. Examples of the ultraviolet transmission inhibitor include i) an ultraviolet transmission inhibitor arranged to shield an optical path or scatter light such as an organic/inorganic filler; talc, silica, a clay, calcium carbonate, and melamine, ii) an ultraviolet transmission inhibitor arranged to shield an optical path such as a carbon/metallic particle; activated carbon, a carbon nanofiller, and a copper powder, iii) an ultraviolet transmission inhibitor arranged to shield an optical path or scatter light such as short/long fiber; potassium titanate, carbon fiber, and glass fiber, iv) an ultraviolet transmission inhibitor arranged to scatter light, refract an optical path, or absorb ultraviolet light such as a polymer/oligomer; polyvinyl chloride, an acrylate resin, an elastomer, and rubber, and v) an ultraviolet transmission inhibitor arranged to shield an optical path, scatter light, or absorb ultraviolet light such as another modifying additive; hydrotalcite, phosphate, borate, and brominated aromatic series.

(46) These substances are added as appropriate in accordance with the intended purpose or desired physical properties of the photosensitive composition. The substance that is infilled or blended in the photosensitive composition in order to provide functions of a cured product is not limited specifically; however, it is preferable that the substance itself should be high in stability from the viewpoint of the intended purpose.

(47) The photosensitive composition can be prepared by blending (A) the ultraviolet curable material, (B) the chain transfer agent, (C) the ultraviolet transmission inhibitor, and the additives. The method for blending these ingredients is not limited specifically; however a method for sufficiently agitating or blending these ingredients to dissolve or uniformly disperse with the use of an agitation equipment such as a blender at appropriate temperature under reduced pressure or in an inert gas atmosphere such as a nitrogen atmosphere is preferably used.

(48) A cured product according to the present invention the photosensitive composition described above that is cured by being irradiated with ultraviolet light.

(49) A method for curing a photosensitive composition that contains an ultraviolet curable material and a chain transfer agent includes making the chain transfer agent transfer a curable activated species that is generated when the photosensitive composition is irradiated with ultraviolet light to a site in the photosensitive composition where the irradiation light does not reach, and chain curing the photosensitive composition whether or not an ultraviolet transmission inhibitor that inhibits ultraviolet transmission exists in the photosensitive composition.

(50) It is also preferable to use visible light instead of ultraviolet light as the irradiation light in the curing. A variety of conventionally known irradiation devices can be used as a UV light irradiation device. In addition, the conditions for the ultraviolet irradiation can be determined as appropriate in accordance with the ultraviolet curable material.

(51) Even in the case of using the photosensitive composition containing (C) the ultraviolet transmission inhibitor, the photosensitive composition can be cured to the inside with the use of an ultraviolet curing reaction by irradiating the photosensitive composition with ultraviolet light irradiation because the chain transfer agent is contained in the photosensitive composition.

(52) In addition, because the chain transfer agent is contained in the photosensitive composition, cured products having a wide variety of shapes can be obtained even when the cured products have shapes such that irradiation light does not reach the cured products.

EXAMPLE

(53) Hereinafter, a description of the present invention will now be specifically provided with reference to Examples and Comparative Examples. The present invention is not limited to these Examples.

Examples 1 to 11, Comparative Examples 1 and 2

(54) Chain transfer agents according to Examples 1 to 11 and materials according to Comparative Examples 1 and 2 are shown in Table 1. The chain transfer agents according to Examples 1 to 12 (B-1 to B12) shown in Table 1 were obtained by preparing the ingredients having the compositions (parts by mass) shown in Table 1, blending the ingredients with the use of an agitation equipment to dissolve or disperse the ingredients. In addition, Comparative Examples 1 and 2 (X-1 and X-2) were obtained by preparing the ingredients (a) without metal-containing compounds contained therein.

(55) TABLE-US-00001 TABLE 1 Comparative Composition of chain transfer Example Example agent (Parts by mass) 1 2 3 4 5 6 7 8 9 10 11 12 1 2 Brevity B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 B-9 B-10 B-11 B-12 X-1 X-2 code Ingredient (a) Containing a UP-1 100 urethane bond UP-2 100 100 100 100 100 100 100 100 100 100 Containing a urea UP-3 100 bond Containing an N3600 100 100 isocyanate group Ingredient (b) metal-containing BPDZ 0.1 0.1 0.1 0.1 0.001 10 0.0005 15 compound CDEDTC 0.1 DBTDL 0.1 BPDC 0.1 BTCN 0.1

(56) The brevity codes shown in Table 1 are described below. The brevity codes with no specific indication of a manufacture are reagent grades manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.

(57) The ingredient (a): a compound containing a urethane bond UP-1: a synthetic compound (Synthetic example 1 will be described later) UP-2: a synthetic compound (Synthetic example 2 will be described later)

(58) The ingredient (a): a compound containing a urea bond UP-3: a synthetic compound (Synthetic example 3 will be described later)

(59) The ingredient (a): a compound containing an isocyanate group

(60) N3600: manufactured by SUMIKA BAYER URETHANE CO. LTD., product name DESMODUR N3600 (the commercialized product was used as the compound containing an isocyanate group.)

Synthetic Example 1

Synthesis of UP-1

(61) 80 g (200 mmol) of polypropylene glycol having a number average molecular weight of 400, 40 g (238 mmol) of hexamethylene diisocyanate, and 0.05 g of dibutyltin dilaurate were put in a reaction container with an agitation equipment, and the liquid temperature of the mixture was heated up to 50 degrees C. from a room temperature for one hour while agitating the mixture. Then, while a small amount of the mixture was sampled to measure its FT-IR to check absorption of an isocyanate group in the vicinity of 2300 cm1, the agitation was continued at 50 degrees C. The content of the residual isocyanate group was calculated based on the absorption area of FT-IR. The moment when the content decreased down to about 15% compared with the content before the reaction and no change was seen was regarded as the completion of the reaction. Thus, a clear and colorless viscous liquid was obtained. This liquid was determined as UP-1. UP-1 defines a compound containing a urethane bond that has a number average molecular weight of 3200 and has an isocyanate group at its terminal.

Synthetic Example 2

Synthesis of UP-2

(62) 100 g (33 mmol) of UP-1, 8.2 g (70.6 mmol) of 2-hydroxyethyl acrylate, 0.05 g of dibutyltin dilaurate, and 0.02 g of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)pro pionate] were put in a reaction container with an agitation equipment, and the liquid temperature of the mixture was heated up to 50 degrees C. from a room temperature for one hour while agitating the mixture. Then, while a small amount of the mixture was sampled to measure its FT-IR to check absorption of an isocyanate group in the vicinity of 2300 cm1, the agitation was continued at 50 degrees C. The content of the residual isocyanate group was calculated based on the absorption area of FT-IR. The moment when the absorption disappeared was regarded as the completion of the reaction. Thus, a clear and colorless viscous liquid was obtained. This liquid was determined as UP-2. UP-2 defines a compound containing a urethane bond that has a number average molecular weight of 3200 and has an acrylate group at its terminal.

Synthetic Example 3

Synthesis of UP-3

(63) 40 g (208 mmol) of 1,11-diamino-3,6,9-trioxaundecane, and 42 g (250 mmol) of hexamethylene diisocyanate were put in a reaction container with an agitation equipment, and the liquid temperature of the mixture was heated up to 50 degrees C. from a room temperature for one hour while agitating the mixture. Then, while a small amount of the mixture was sampled to measure its FT-IR to check absorption of an isocyanate group in the vicinity of 2300 cm1, the agitation was continued at 50 degrees C. The content of the residual isocyanate group was calculated based on the absorption area of FT-IR. The moment when the content decreased down to about 15% compared with the content before the reaction and no change was seen was regarded as the completion of the reaction. Thus, a clear and colorless viscous liquid was obtained. This liquid was determined as UP-3. UP-3 defines a compound containing a urea bond that has a number average molecular weight of 2000 and had an isocyanate group at its terminal.

(64) The ingredient (b): a metal-containing compound BPDZ: bis(2,4-pentanedionato)zinc(II) CDEDTC: zinc (II) diethyldithiocarbamate DBTDL: dibutyltin dilaurate BPDC: bis(2,4-pentanedionato)cobalt(II) BTCN: nickel (II) dibutyldithiocarbamate

Examples 2-1 to 2-19, Comparative Examples 2-1 to 2-6

(65) Hereinafter, Examples and Comparative Examples of the photosensitive compositions are shown. The ultraviolet curable materials (A-1 to A-4) shown in Table 2 were used for Examples and Comparative Examples of the photosensitive compositions.

(66) The ingredients shown in Table 2 are described below.

(67) [(Meth)acrylate] IBA: isobornyl acrylate DPGA: dipropylene glycol diacrylate UP-2: a synthetic compound (described in Synthetic example 2)

(68) [Ultraviolet(photo) Polymerization Initiator] HCHPK: 1-hydroxycyclohexyl phenyl ketone EANT: 2-ethyl anthraquinone

(69) TABLE-US-00002 TABLE 2 Composition of an ultraviolet curable material (Parts by mass) A-1 A-2 A-3 A-4 (Meth)acrylate IBA 100 DPGA 100 100 UP-2 100 Photo HCHPK 2 2 2 polymerization EANT 2 initiator

(70) The photosensitive compositions according to Examples 2-1 to 2-19 were prepared by adding the chain transfer agents according to Examples 1 to 12 (B-1 to B-12) having the respective contents shown in Table 1 to the ultraviolet curable materials of A-1 to A-4 shown in Table 2, and tests to evaluate a curing property were performed on the photosensitive compositions. In addition, Comparative Examples 2-1 to 2-6 were prepared from the materials shown in Table 4, for comparison, and tests to evaluate a curing property were performed on Comparative Examples 2-1 to 2-6.

Comparative Example 2-1

(71) The test was performed on Comparative Example 2-1 that was made only from the ultraviolet curable material of A-2 shown in Table 2.

Comparative Example 2-2

(72) The test was performed on Comparative Example 2-2 that was made only from the chain transfer agent (B-1) according to Example 2.

Comparative Example 2-3

(73) The test was performed on Comparative Example 2-3 in a same manner as the test on Example 2-2 except that Comparative Example 2-3 was made from the material according to Comparative Example 1 (X-1) instead of using the chain transfer agent (B-2) according to Example 2-2.

Comparative Example 2-4

(74) The test was performed on Comparative Example 2-4 in a same manner as the test on Example 2-2 except that Comparative Example 2-4 was made from the material according to Comparative Example 2 (X-2) instead of using the chain transfer agent (B-2) according to Example 2-2.

Comparative Example 2-5

(75) The test was performed on Comparative Example 2-5 in a same manner as the test on Example 2-2 except that Comparative Example 2-5 was made from 2-mercaptobenzimidazole (MBI) that was a known chain transfer agent instead of using the chain transfer agent (B-2) according to Example 2-2. MBI is an example of a chain transfer agent containing a mercapto group that is described in Non-patent document 1 above.

Comparative Example 2-6

(76) The test was performed on Comparative Example 2-6 in a same manner as the test on Example 2-2 except that comparative example 2-6 was made from 2,4-diphenyl-4-methyl-1-pentene (DPMP) that was a known chain transfer agent instead of using the chain transfer agent (3-2) according to Example 2-2. DPMP is an example of a chain transfer agent having an -methylstyrene dimer structure that is described in Patent document 7 above.

(77) Results of the tests are shown in Tables 3 and 4. Detailed descriptions of the compositions and the test method to evaluate a curing property shown in Tables 3 and 4 will be provided below.

(78) (Test Method for Evaluating a Curing Property)

(79) Each of the ultraviolet curable compositions was put in a glass tube having an inner diameter of 5 mm and a height of 50 mm such that the fluid level was 20 mm high, and was ultraviolet irradiated for ten seconds from the side with the use of a UV lamp (100 mW/cm2, manufactured by SEN LIGHTS CO., LTD.). Then, each of the ultraviolet curable compositions was left for one minute at room temperature, and then a glass rod having a diameter of 1.5 mm was inserted from the top to check with finger touch whether or not each of the ultraviolet curable compositions was cured. The ultraviolet curable compositions into which the glass rod could not be inserted below the fluid level were regarded as cured and rated passed, and the ultraviolet curable compositions into which the glass rod could be easily inserted below the fluid level were regarded as uncured and rated failed.

(80) (Measurement Method for Measuring a Distance to a Cured Dark Portion)

(81) Each of the ultraviolet curable compositions was put in a glass tube having an inner diameter of 5 mm and a height of 50 mm such that the fluid level was 20 mm high. The upper half (10 mm) of each content in the glass tube was wrapped with an aluminum foil to make a light-shielded portion. Then, each of the ultraviolet curable compositions was ultraviolet irradiated for ten seconds from the side with the use of a UV lamp (100 mW/cm2, manufactured by SEN LIGHTS CO., LTD.). Then, each of the ultraviolet curable compositions was left for twenty minutes at room temperature, and then a glass rod having a diameter of 1.5 mm was inserted from the top to check the cured portion, and the distance to each cured portion that proceeded to the upper portion (unirradiated portion) from the border between the ultraviolet irradiation face and the light-shielded face was measured. The evaluation to evaluate whether or not the ultraviolet curable compositions were cured was performed in a same manner as the evaluation performed in the test method for evaluating a curing property.

(82) TABLE-US-00003 TABLE 3 Example 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 2-9 2-10 Ingredient composition (Parts by mass) Ultraviolet curable A-1 60 material A-2 60 60 60 60 60 60 60 A-3 60 A-4 60 Chain transfer agent B-1 40 B-2 40 40 40 40 B-3 40 B-4 40 B-5 40 B-6 40 B-7 40 B-8 B-9 B-10 B-11 B-12 Test result Curing property Passed Passed Passed Passed Passed Passed Passed Passed Passed Passed Distance to a cured >9.5 >9.5 8.6 >9.5 >9.5 8.6 9 7.6 7.3 6.8 dark portion (mm) Example 2-11 2-12 2-13 2-14 2-15 2-16 2-17 2-18 2-19 Ingredient composition (Parts by mass) Ultraviolet curable A-1 material A-2 60 60 60 60 60 90 10 95 5 A-3 A-4 Chain transfer agent B-1 B-2 10 90 5 95 B-3 B-4 B-5 B-6 B-7 B-8 40 B-9 40 B-10 40 B-11 40 B-12 40 Test result Curing property Passed Passed Passed Passed Passed Passed Passed Passed Passed Distance to a cured 5.2 3.8 3.4 2.8 2.9 4.5 4.7 2.4 2.8 dark portion (mm)

(83) TABLE-US-00004 TABLE 4 Comparative Example 2-1 2-2 2-3 2-4 2-5 2-6 Ingredient composition (Parts by mass) Ultraviolet A-2 100 60 60 60 60 curable material Chain transfer B-2 100 agent C-1 40 C-2 40 MBI 40 DPMP 40 Test result Curing property Passed Failed Passed Passed Passed Passed Distance to a cured dark 0.5> 0.5> 0.5> 0.5> 0.5> portion (mm)

(84) As shown in Table 3, it was confirmed that all of the photosensitive compositions according to Examples 2-1 to 2-19 had a favorable curing property. In addition, among the photosensitive compositions according to Examples 2-1 to 2-19, the photosensitive composition that had the shortest distance to the cured dark portion was 2.4 mm (Example 2-16), whereby it was confirmed that the photosensitive compositions containing the chain transfer agents according to present Examples had a dark portion curing property.

(85) Meanwhile, Comparative Example 2-1 had a distance to the cured dark portion shorter than 0.5 mm because Comparative Example 2-1 is made only from the ultraviolet curable material and does not contain the chain transfer agent.

(86) In addition, as shown in Table 4, curing by ultraviolet light was not confirmed in the photosensitive composition according to Comparative Example 2-2 because the photosensitive composition according to Comparative Example 2-2 did not contain the ultraviolet curable material. That is, it was shown that the ultraviolet curable material that contained the (meth)acrylate ingredient and the photo polymerization initiator was necessary for the initial curing, and the ultraviolet curable material that was made only from the chain transfer agent could not be cured. Meanwhile, all of the photosensitive composition according to Example 2-1 to 2-4, which contained the chain transfer agent according to Comparative Example 2-2, contained also the ultraviolet curable materials, so that all of the photosensitive composition according to Example 2-1 to 2-4 were cured by ultraviolet irradiation.

(87) In addition, Comparative Examples 2-3 and 2-4 had distances to the cured dark portions less than 0.5 mm, which meant that the curing of the dark portions hardly proceeded. Comparative Examples 2-3 and 2-4 contained the materials of Comparative Examples 1 and 2 (X-1 and X-2) that were made only from the ingredient (a) and did not contain the metal-containing compound of the ingredient (b), instead of containing the chain transfer agent according to Example 2-2. From this result, it was shown that the chain transfer agent needed to contain the ingredient (a) that was the compound containing the urethane bond, the urea bond or the isocyanate group, and the ingredient (b) that was the metal-containing compound in order to provide a dark portion curing property to the ultraviolet curable material.

(88) The chain transfer agent according to the present invention is capable of transferring radicals generated by ultraviolet irradiation to a site such as a dark portion where radicals are not generated, and initiating to progress a radical polymerization reaction in the ultraviolet curable material. Thus, the chain transfer agent according to the present invention has the function of retaining the generated radicals for a certain period of time (hereinafter, the function is referred to as a radical retention capacity). A test to check the radical retention capacity of the chain transfer agent according to the present invention was performed.

(89) [Test Method for Checking a Radical Retention Capacity]

(90) Radicals in a substance can be detected with the use of an electron spin resonance (ESR) device, so that the detection of the radicals retained in the chain transfer agent were made by the method shown below in (1) to (5) to see the lifetime of the radicals.

(91) (1) The ultraviolet curable material (A-2) shown in Table 2 was put in a glass tube having an inner diameter of 5 mm and a height of 50 mm such that the fluid level was 20 mm high.

(92) (2) Then, the chain transfer agent (B-2) according to Example 2 shown in table 1 was gently added to the ultraviolet curable material from the top to the inside of the glass tube with the use of a micropipette to prepare a liquid of two layers consisting of the ultraviolet curable material and the chain transfer agent.

(93) (3) The two-layered liquid was ultraviolet irradiated for ten seconds with the use of a UV

(94) (ultraviolet) lamp (100 mW/cm2, manufactured by SEN LIGHTS CO., LTD.).

(95) (4) After the ultraviolet irradiation, by quickly separating the chain transfer agent, 20 L of measurement sample was sampled from the separated chain transfer agent, and ESR measurement was performed on the measurement sample after two minutes from the ultraviolet irradiation. Conditions of measurement were JES-FA 200, POWER 2.0 mW, SWEEP TIME 30 sec.

(96) (5) After leaving the measurement sample more two hours at room temperature, ESR measurement was performed on the measurement sample under the same conditions as the above-described measurement made after two minutes from the ultraviolet irradiation.

(97) It is to be noted that for comparison, tests to evaluate a radical retention capacity were performed in the same manner as above also on the compound containing the isocyanate group (X-2) according to Comparative Example 2 shown in Table 1, and 2,4-diphenyl-4-methyl-1-pentene (DPMP) that was a known chain transfer agent.

(98) [Concerning Results of the Tests to Evaluate a Radical Retention Capacity]

(99) FIG. 1 is a chart showing a result of the ESR measurement of the chain transfer agent (B-2) according to Example 2. As shown in the chart of FIG. 1, in the chain transfer agent (B-2) according to Example 2, four organic radical peaks were detected in the vicinities of g values of 2.023, 2.009, 2.005, and 1.986 in the ESR measurement made after two minutes from the ultraviolet irradiation.

(100) FIG. 2 is a graph showing a relation between a measurement peak strength and an amount of time when the chain transfer agent is left at room temperature in relation to the ESR measurement results of the above-described three kinds of samples. As shown in FIG. 2, in the chain transfer agent (B-2) according to Example 2, the peak strength of the organic radicals attenuated only up to 80% even after two hours from the ultraviolet irradiation. From this result, it was shown that the chain transfer agent according to the present invention was capable of retaining the radicals in a stable manner for a long time. That is, it was confirmed that adding the chain transfer agent according to the present invention to the ultraviolet curable material allowed the radicals that were generated by the ultraviolet irradiation to be dispersed in the ultraviolet curable material via the chain transfer agent according to the present invention to cure the dark portion that the irradiation light does not reach.

(101) In addition, as shown in the ESR measurement results in the chart of FIG. 2, in the compound containing the isocyanate group (C-2) according to Comparative Example 2, a peak of the organic radicals could not be detected at all even after two minutes from the ultraviolet irradiation. This result confirmed that only the compound containing the isocyanate group (C-2) could not retain the radicals, so that the dark portion could not be cured.

(102) In addition, as shown in the ESR measurement results in the chart of FIG. 2, in the commercially available known chain transfer agent DMPA, a trace of a peak of the organic radicals was seen after two minutes from the ultraviolet irradiation; however, a peak of the organic radicals disappeared completely after two hours from the ultraviolet irradiation. From this result, it was shown that the radical retention capability of the DPMA was weak, and even if the DPMA once received the radicals, the radicals disappeared instantly, so that the radicals could not reach the dark portion. As shown in the results described above, it was shown that the chain transfer agent according to the present invention had the radical retention capability that had never seen in a conventional chain transfer agent, and the dark portion that ultraviolet light did not reach could be cured by this capability.

Examples 3-1 to 3-16, Comparative Example 3-1, 3-2

(103) As shown in FIGS. 5 and 6, curing percentages of deep portions of photosensitive compositions that contained the ultraviolet curable materials (A-1 and A-2) shown in Table 1, the chain transfer agents (B-2 to B-12) shown in Table 2, and ultraviolet transmission inhibitors that defined any one of 30 parts by mass of talc (Talc), 30 parts by mass of carbon nanotube (VGCF), 30 parts by mass of polyvinyl chloride (PVC), and 300 parts by mass of polyvinyl chloride (PVC) were measured. It is to be noted that for comparison, as shown in Table 6, a curing percentage of a deep portion of a composition (Comparative Example 3-1) that contained the ultraviolet curable material (A-1) and an ultraviolet transmission inhibitor, and a curing percentage of a deep portion of a composition (Comparative Example 3-2) that contained the ultraviolet curable material (A-2) and an ultraviolet transmission inhibitor, the compositions being examples of compositions that did not contain the chain transfer agent, were measured in the same manner as the Examples described above. The test results are shown in Tables 5 and 6.

(104) TABLE-US-00005 TABLE 5 Example 3-1 3-2 3-3 3-4 3-5 3-6 3-7 3-8 3-9 3-10 3-11 Ingredient composition (Parts by mass) Ultraviolet curable A-1 60 material A-2 60 60 60 60 60 60 60 60 60 60 Chain transfer agent B-2 40 40 B-3 40 B-4 40 B-5 40 B-6 40 B-7 40 B-8 40 B-9 40 B-10 40 B-11 40 B-12 Test result Curing 30 parts by 1 mm >98% >98% >98% >98% >98% >98% >98% >98% >98% >98% >98% percentages mass of Talc 20 mm >98% >98% >98% >98% >98% >98% >98% >98% >98% >98% 97% of 30 parts by 1 mm >98% >98% >98% >98% >98% >98% >98% >98% >98% >98% >98% deep mass of VGCF 20 mm 92% 95% 95% 95% 93% 92% 91% 90% 88% 87% 86% portions 30 parts by 1 mm >98% >98% >98% >98% >98% >98% >98% >98% >98% >98% >98% mass of PVC 20 mm >98% >98% >98% >98% >98% >98% >98% 96% 96% 96% 90% 300 parts by 1 mm >98% >98% >98% >98% >98% >98% >98% >98% >98% >98% >98% mass of PVC 20 mm >98% >98% >98% >98% >98% >98% 97% 94% 93% 92% 88%

(105) TABLE-US-00006 TABLE 6 Comparative Example Example 3-12 3-13 3-14 3-15 3-16 3-1 3-2 Ingredient composition (Parts by mass) Ultraviolet curable material A-1 100 A-2 60 90 10 95 5 100 Chain transfer agent B-2 10 90 5 95 B-3 B-4 B-5 B-6 B-7 B-8 B-9 B-10 B-11 B-12 40 Test result Curing 30 parts by mass 1 mm >98% >98% >98% >98% >98% 85% 87% percentages of Talc 20 mm 97% >98% >98% 96% 96% Failed Failed of 30 parts by mass 1 mm >98% >98% >98% 96% 95% 25% 26% deep of VGCF 20 mm 88% 88% 88% 86% 86% Failed Failed portions 30 parts by mass 1 mm >98% >98% >98% >98% >98% 89% 92% of PVC 20 mm 91% >98% >98% 93% >98% 1%> 1%> 300 parts by 1 mm >98% >98% >98% >98% >98% 76% 79% mass of PVC 20 mm 88% 94% 95% 87% 88% 1%> 1%>

(106) A specific method for preparing the photosensitive compositions and cured products shown in Tables 5 and 6 is described below. A predetermined amount of each of Talc, VGCF, and PVC shown in Tables 5 and 6 were added as infilling/blending materials (ultraviolet transmission inhibitors) to 100 parts by mass of composition containing the chain transfer agent and the ultraviolet curable material that were yet to be blended, and tests to evaluate a dark portion curing property were performed on the compositions. The abbreviated expressions in Tables 5 and 6 are as follows. The abbreviated expressions with no specific indication of a manufacture are reagent grades manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD. Talc: talc (13 m in particle diameter) (manufactured by NIPPON TALC CO., LTD., MS-P) VGCF: carbon nanotube (150 nm in diameter) (manufactured by SHOWA DENKO K.K., VGCF-H) PVC: polyvinyl chloride (n=1100) (manufactured by WAKO PURE CHEMICAL INDUSTRIES, LTD.)

(107) (Preparation of Compositions Yet to be Blended)

(108) The ultraviolet curable materials (A-1 and A-2) and the chain transfer agents (B-2 to B-12) shown in Table 2 were blended so as to have the ratios (parts by mass) shown in Tables 5 and 6 with the use of an agitation equipment, and dissolved or dispersed. Thus, the compositions yet to be blended were prepared.

(109) (Preparation of Infilled/Blended Photosensitive Compositions)

(110) Each of 30 parts by mass of Talc and 30 parts by mass of VGCF was added to 100 parts by mass of the composition yet to be blended, and each composition was blended with the use of an agitation equipment such that each of Talc and VGCF was uniformly dispersed and infilled in the composition. The talc infilled photosensitive composition was a white viscous liquid, and the VGCF infilled photosensitive composition was a black viscous liquid.

(111) The PVC compound was not dispersed just by being agitated as it was, so that the following method was used to blend the PVC compound.

(112) 1) A PVC resin was dissolved in THF at 40 degrees C., and a solution of 30% was prepared.

(113) 2) The solution prepared in 1) of the amount corresponding to 30 or 300 parts by mass of PVC was added to 100 parts by mass of each of the compositions yet to be blended, and was blended with the use of an agitation equipment to be uniformly dissolved.

(114) 3) The compositions were left while shielded at 40 degrees C. for thirty-six hours to volatilize THF. Thus, lumps of PVC-blended photosensitive compositions each having a thickness of 3 cm were obtained.

(115) The PVC-blended photosensitive compositions were white rubber-like solid substances. The PVC-blended photosensitive compositions containing 300 parts by mass of PVC were stronger in whiteness.

(116) (Ultraviolet Curing)

(117) Because the Talc infilled photosensitive compositions and VGCF infilled photosensitive compositions had a flow property, each of the Talc infilled photosensitive compositions and the VGCF infilled photosensitive compositions was put in a hard Teflon tube (Teflon is a registered trademark) having an inner diameter of 10 mm such that the fluid level was 30 mm high, and was cured by being ultraviolet irradiated for ten seconds from the above with the use of a UV lamp (100 mW/cm2, manufactured by SEN LIGHTS CO., LTD.). The cured products were left in the tubes and stored at room temperature in a dark room.

(118) Because the PVC-blended photosensitive compositions had no flow property, each lump of the prepared compositions was cut to have a cross section of 1 mm1 mm and a height of 30 mm, and was cured by being ultraviolet irradiated for ten seconds from the above with the use of a UV lamp (100 mW/cm2, manufactured by SEN LIGHTS CO., LTD.). The cured products were stored at room temperature in a dark room.

(119) (Test Method for Measuring a Curing Percentage of a Deep Portion)

(120) A curing percentage was measured by determining quantity of the residual quantity of FT-IR of double bonds of an acrylate that related to curing polymerization in each ultraviolet curable material. The measurement method is described below. FIG. 3 is a chart showing a measurement result of FT-IR of the double bonds of the acrylate. As shown in FIG. 3, unsaturated double bonds of the acrylate have special infrared absorption at 811 cm-1 (Aa absorption at the peak before curing shown in FIG. 3). When the acrylate is cured completely, the double bonds of the acrylate are consumed, so that the peak disappears. In addition, amido NH bonds that have no relation with the polymerization reaction of the acrylate have absorption in the vicinity of 775 cm-1 (Ab absorption at the peak before curing shown in FIG. 3). A percentage of curing reaction can be calculated by obtaining the ratio Aa/Ab between a spectral area Aa and spectral area Ab, and comparing the obtained ratio with the ratio Aa/Ab at 0% curing and the ratio Aa/Ab at 100% curing that have been measured in advance. Table 7 shows relative areas at the peaks in the graph of FIG. 3. As shown in Table 7, the ratio Aa/Ab at 0% curing that is the lowest is 5.585, the ratio Aa/Ab at 100% curing that is the top is 0, and the ratio Aa/Ab at the peak that is at the midpoint is 5.585, so that the percentage of curing reaction of 82% can be calculated by the following mathematical expression.
Percentage of curing reaction=(5.5851.006)/5.585100=82%

(121) TABLE-US-00007 TABLE 7 Relative area Aa Ab Aa/Ab 100% curing 0 508 0 82% curing 468 465 1.006 0% curing 1413 253 5.585

(122) The curing percentages of the infilled/blended photosensitive compositions that were cured by ultraviolet irradiation defined curing percentages in the vicinity of the irradiation surfaces that were measured on cross sections at the depth of 1 mm from the irradiation surfaces, and curing percentages of the dark portions measured on cross sections at the depth of 20 mm from the irradiation surfaces. The FT-IR on the cross sections was measured to obtain Aa/Ab, and the curing percentages (%) were calculated based on the Aa/Ab and shown in Tables 5 and 6. The photosensitive compositions that were not cured and could not be sampled were rated as failed. In this case, the curing percentage was less than 1%.

Evaluation Results, Examples 3-1 to 3-16, and Comparative Examples 3-1 and 3-2

(123) The photosensitive compositions according to Comparative Examples 3-1 and 3-2 did no t contain the chain transfer agent, so that when the Talc, VGCF and PVC were infilled/blended in the photosensitive compositions, attenuation of the curing percentages was seen even in the depth of 1 mm from the surfaces, and curing by ultraviolet irradiation was not seen in the depth of 20 mm. It was shown that in the dark portion curing of photosensitive compositions containing the ultraviolet transmission inhibitors, the amounts of ultraviolet light necessary for curing became insufficient from the vicinity of the irradiation surfaces, and no cured product was obtained in the depth of 20 mm.

(124) Meanwhile, it was confirmed that in the photosensitive compositions according to Examples 3-1 to 3-16 that contained the chain transfer agents, the curable activated species (radicals) that were generated on the irradiation surfaces dispersed into the deep portions, so that curing percentages of 85% or more could be obtained even in the depth of 20 mm only by the ultraviolet irradiation.

Example 3-17, and Comparative Example 3-3

(125) Evaluation of a PVC Blended Photosensitive Sheet

(126) Usually when an ultraviolet curable material and polymer are blended, they become a white clouded material because they are different in dissolution parameter (SP value) and refraction index, so that ultraviolet transmission is inhibited to cause insufficient curing. In order to solve this problem, a test to verify that a sheet having a sufficient curing property could be produced by using the photosensitive composition according to the present invention in which PVC that functioned as flexible polymer was contained was performed.

(127) (Production of a Sheet Made from a PVC Blended Photosensitive Composition)

(128) (a) A PVC resin was dissolved in THF at 40 degrees C., and a solution of 30% was prepared.

(129) (b) The solution prepared in the (a) step of the amount corresponding to 300 parts by mass of PVC was added to 100 parts by mass of composition yet to be blended according to Example 3-2 (Table 5) in a beaker, and was blended with the use of an agitation equipment to be uniformly dissolved (Example 3-17, a composition before drying).

(130) (c) A solution that was a comparative example different from the solution prepared in the (b) step in containing the composition yet to be blended according to Comparative Example 3-2 (Table 6) was prepared Comparative Example 3-3, a composition before drying).

(131) (d) each of 165 g of the solution prepared in the (b) step (Example 3-17, a composition before drying) (containing 60 g of the photosensitive composition), and 165 g the solution prepared in the (c) step (Comparative Example 3-3, a composition before drying) (containing 60 g of the photosensitive composition) was put in a 200 mm300 mm stainless tray, and uniformly flattened, and then dried at room temperature for two days while shielded. Thus, white sheets having a thickness of 1 mm were prepared (Example 3-17 and Comparative Example 3-3). Both of the sheets according to Example 3-17 and Comparative Example 3-3 were flexible rubber-like sheets that were capable of stretching.

(132) (Curing of a Sheet Made from a PVC Blended Photosensitive Composition)

(133) Each of the sheets according to Example 3-17 and Comparative Example 3-3 was wound around a wire bundle 2 cm in diameter, and was ultraviolet irradiated from two lateral sides for ten seconds per side with the use of a UV lamp (100 mW/cm2, manufactured by SEN LIGHTS CO., LTD.), and then left to be cooled in a dark room for ten minutes.

Evaluation Results, Example 3-17, and Comparative Example 3-3

(134) The sheet according to Example 3-17 was uniformly cured and could not be bent after the ultraviolet irradiation while the sheet according to Comparative Example 3-3 could be easily bent even after the ultraviolet irradiation. It was obvious that in the sheet according to Comparative Example 3, the ultraviolet irradiation was inhibited by the influence of light scattering caused by the PVC contained in the photosensitive composition, so that the curing did not proceed uniformly.

(135) Meanwhile, it was confirmed that according to Example 3-17, the uniformly cured product could be produced from the photosensitive composition containing the chain transfer agent only by the ultraviolet irradiation even when the photosensitive composition is a PVC mixture in which ultraviolet transmission is inhibited by the influence of light scattering, whereby a curing material in the form of a sheet or a tape could be produced.

(136) That is, a photosensitive composition that can directly wrap or be adhered to an object and thereby is made easier to handle can be produced easily.

Examples 4-1 to 4-10, and Comparative Examples 4-1 and 4-2

(137) Hereinafter, photosensitive compositions according to Examples 4-1 to 4-10, and Comparative Examples 4-1 and 4-2 will be described, each of which contains a polyisocyanate compound having two or more isocyanate groups, (meth)acrylate of a polyol having one or less hydroxyl group, the number of which is set by ester bonding two or more hydroxyl groups of and the polyol having two or more hydroxyl groups with the (meth)acrylate, and an ultraviolet polymerization initiator.

(138) Curable liquid compositions having the ingredient compositions (parts by mass) shown in Table 8 were prepared by blending the ingredients with the use of an agitation equipment to dissolve or disperse. The ingredients are described below. Evaluations to evaluate a curing property and a dark portion curing property were performed in accordance with the following measurement method and evaluation method. The results of the evaluations are shown in Table 8 together with the ingredient compositions.

(139) <(Meth)acrylate Ingredient> DPGA: [Dipropylene glycol diacrylate manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.] TEGDA: [Tetraethylene glycol diacrylate manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.] AMPOH: [1-acryloyloxy-3-methacryloyloxy-2-propanol(2-hydroxy-3-acryloyloxy propyl methacrylate) manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.]

(140) (Ultraviolet polymerization initiator) HCHPK: [1-hydroxycyclohexyl phenyl ketone manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.] EANT: [2-ethyl anthraquinone manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.]

(141) (Polyisocyanate compound) N3600: [DESMODUR N3600 manufactured by SUMIKA BAYER URETHANE CO., LTD.] N3200: [DESMODUR N3200 manufactured by SUMIKA BAYER URETHANE CO., LTD.]

(142) (Metal complex compound) BPDZ: (Bis(2,4-pentanedionato)zinc(II) manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.] CDEDTC: (Zinc (II) diethyldithiocarbamate manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.] DBTDL: (dibutyltindilaurate manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.]

(143) (Curing Property)

(144) Each of the curable liquid compositions was put in a glass tube having an inner diameter of 5 mm and a height of 50 mm such that the fluid level was 20 mm high, and was ultraviolet irradiated for ten seconds from the side with the use of a UV lamp (100 mW/cm2, manufactured by SEN LIGHTS CO., LTD.). Then, each of the curable liquid compositions was left for one minute at room temperature, and then a glass rod having a diameter of 1.5 mm was inserted from the top to check with finger touch whether or not each of the curable liquid compositions was cured. The curable liquid compositions into which the glass rod could not be inserted below the fluid level were regarded as cured and rated passed, and the curable liquid compositions into which the glass rod could be easily inserted below the fluid level were regarded as uncured and rated failed.

(145) (Dark Portion Curing Property)

(146) Each of the curable liquid compositions was put in a glass tube having an inner diameter of 5 mm and a height of 50 mm such that the fluid level was 20 mm high. The upper half (10 mm) of each content in the glass tube was wrapped with an aluminum foil to make a light-shielded portion. Then, each of the curable liquid compositions was ultraviolet irradiated for ten seconds from the side with the use of a UV lamp (100 mW/cm2, manufactured by SEN LIGHTS CO., LTD.). Then, each of the curable liquid compositions was left for one minute at room temperature and left for one hour at room temperature, and then a glass rod having a diameter of 1.5 mm was inserted from the top to check the cured portion, and the distance to each cured portion that proceeded to the upper portion (unirradiated portion) from the border between the ultraviolet irradiation face and the light-shielded face was measured. The evaluation to evaluate whether or not the curable liquid compositions were cured was performed in a same manner as the evaluation performed in the test method for evaluating a curing property.

(147) TABLE-US-00008 TABLE 8 Comparative Example Example 4-1 4-2 4-3 4-4 4-5 4-6 4-7 4-8 4-9 4-10 4-1 4-2 (Meth)acrylate DPGA 50 50 50 50 50 50 8 92 100 TEGDA 50 AMPOH 50 Ultraviolet HCHPK 3 3 3 3 3 3 3 3 3 3 3 polymerization EANT 3 initiator Polyisocyanate N3600 50 50 50 50 50 50 50 92 8 100 compound N3200 50 Metal complex BPDZ 0.5 0.5 0.5 5 0.5 5 0.5 5 0.5 compound CDEDTC 0.5 DBTDL 0.5 Curing property Passed Passed Passed Passed Passed Passed Passed Passed Passed Passed Passed Failed Distance to a cured 9.5 7.8 6.9 9.4 9 8.6 6.4 1.9 2.4 1.3 0.5 dark portion (mm) after 1 min Distance to a cured 10< 10< 10< 10< 10< 10< 10< 6.8 7.3 5.1 0.5 dark portion (mm) after 1 hr

(148) In the evaluation on a curing property, curing by ultraviolet light was not seen in the curable liquid composition according to Comparative Example 4-2 because the curable liquid composition according to Comparative Example 4-2 did not contain the (meth)acrylate ingredient. That is, it was shown that the (meth)acrylate ingredient was necessary for the initial curing, and the curable liquid composition could not be cured even if the other ingredients were sufficiently contained therein. Meanwhile, it was confirmed that all of the curable liquid compositions according to the present Examples were cured by ultraviolet irradiation, and cured products were produced.

(149) In the evaluation on a dark portion curing property, curing of a dark portion hardly proceeded in the curable liquid composition according to Comparative Example 4-1 even after the curable liquid composition according to Comparative Example 4-1 was left for one hour at room temperature. This meant that curing hardly proceeded because the curable liquid composition according to Comparative Example 4-1 did not contain the polyisocyanate ingredient.

(150) Meanwhile, the curable liquid compositions according to Examples 4-1 to 4-10 had distances to the cured dark portion that are equal to or longer than 5 mm to the unirradiated portions from the borders between the ultraviolet irradiation faces and the light-shielded faces. Thus, the dark portion curing properties of the curable liquid compositions according to Examples 4-1 to 4-10 were confirmed.

(151) As described above in the Examples, the cured products can be made from the photosensitive composition containing the polyisocyanate compound, the (meth)acrylate of the specific polyol, and the ultraviolet polymerization initiator by ultraviolet irradiation. In addition, not only the cured product in which a portion that is irradiated with ultraviolet light is cured can be obtained, but also the cured product in which a portion that ultraviolet light does not reach (dark portion) is cured can be obtained. Therefore, according to the present invention, the portion of the composition that light does not reach (dark portion) can be cured while the composition maintains the advantage of an ultraviolet curing property of being curable in a short time.

(152) It is presumed that the (meth)acrylate of the specific polyol is radical reacted by the ultraviolet polymerization initiator when the composition is irradiated with ultraviolet light, and at this time, reaction activated species that cure the polyisocyanate compound are generated from the (meth)acrylate of the specific polyol to disperse, whereby the polyisocyanate compound in the dark portion is cured.

(153) In addition, in the photosensitive composition described above, the number of hydroxyl group of the (meth)acrylate of the specific polyol is set to be one or less, so that a urethane reaction of the (meth)acrylate of the specific polyol with the polyisocyanate compound is inhibited from proceeding in the state of being blended with the polyisocyanate compound. Thus, preservation stability of the present composition is improved. The number of hydroxyl group of the (meth)acrylate of the specific polyol is preferably one or zero. It is more preferable that the number of hydroxyl group of the (meth)acrylate of the specific polyol should be zero from the viewpoint of preservation stability of the present composition.

(154) Considering that the effects of the present invention are easily achieved, dipropylene glycol diacrylate, tetraethyl ene glycol diacrylate, or 1-acryloyl oxy-3-methacryloyloxy-2-propanol (2-hydroxy-3-acryloyloxy propyl methacrylate) is preferably used as the (meth)acrylate of the specific polyol.

(155) The (meth)acrylate of the specific polyol is contained in the photosensitive composition at the ratio between the polyisocyanate compound and the (meth)acrylate of the specific polyol preferably within a range from 90:10 to 10:90 at a mass ratio, and more preferably within a range from 80:20 to 20:80 at a mass ratio. When the content of the (meth)acrylate of the specific polyol is more than 90, the content is too large to the content of the polyisocyanate compound, so that the amount of the polyisocyanate compound that is in charge of curing reaction becomes insufficient, whereby the curing speed in the dark portion tends to be reduced. On the other hand, also when the content of the (meth)acrylate of the specific polyol is less than 10, the amount of the generated activated species that cure the polyisocyanate compound becomes insufficient, whereby the curing speed in the dark portion tends to be reduced.

(156) In addition, the content of the ultraviolet polymerization initiator is preferably within a range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the mixture of the polyisocyanate compound and the (meth)acrylate of the specific polyol, and more preferably within a range of 0.1 to 7 parts by mass. When the content of the ultraviolet polymerization initiator is less than 0.01 parts by mass, the amount of the ultraviolet polymerization initiator is too small, whereby a curing reaction by ultraviolet light is not easily initiated. On the other hand, when the content of the ultraviolet polymerization initiator is more than 10 parts by mass, an insoluble matter is generated, whereby the physical properties of the cured product could be lost.

(157) In addition, it is preferable that the photosensitive composition should further contain a metal complex compound. When the metal complex compound is contained in the photosensitive composition, the curing speed at the dark portion can be further improved.

(158) Examples of the metal complex compound include the metal complex compounds of the photosensitive composition described above. Examples of the metal complex compound include metals selected from the group consisting of tin, copper, zinc, cobalt, and nickel.

(159) The content of the metal complex compound is preferably within a range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the mixture of the polyisocyanate compound and the (meth)acrylate of the specific polyol, and more preferably within a range of 0.05 to 5 parts by mass. When the content of the metal complex compound is less than 0.01 parts by mass, the amount of the metal complex compound is too small, whereby the photosensitive composition becomes less effective in improving the curing speed in the dark portion. On the other hand, when the content of the metal complex compound is more than 10 parts by mass, an insoluble matter is generated, whereby preservation stability of the present composition could be decreased, or the physical properties of the cured product could be lost.

(160) The foregoing description of the preferred embodiments of the present invention has been presented for purposes of illustration and description; however, it is not intended to be exhaustive or to limit the present invention to the precise form disclosed, and modifications and variations are possible as long as they do not deviate from the principles of the present invention.